Silver halide emulsion containing twoequivalent yellow dye-forming coupler



June 3, 1969 LORIA 3,447,928

SILVER HALIDE EMULSION CONTAINING TWO-EQUIVALENT YELLOW DYE-FORMING COUPLER Filed July 26, 1965 Sheet of 2 I I I 2 1 I i I CURVE 1 IMAGE FROM COATING ICONTNNING COUPLER oL-[3-[d-( fll;(l 3l-TERT mzmxv) BUTYRAMI asnzon. 2- msmoxmcsmmuo: CURVE 2 IMAGE FROM commsasme AS comma; BUT VzTHE I AMOUNT OF A9 I 9 'CURVE 3 IMAGE FROM COATING a 4 commms a-Ac ETOXYd- {a-[d-(Zfi-Dl-TERTfliMYL- a T PHENOXY) au'rYRAmoo] a BEnzoYL}-2-METHox-/Acs1'- CURVE wt -77 ANILIDE wn'n '/2THE AMOUNI' E or Ag in camns 1 w". L.V-. .W .r l.. t I F F I I Z Lu Q I .W .i 10 h .m HA 1,. i "um. L 8

,X Y/// 22x" I P EXPOSURE STEP Anihony Loria IN V EN TOR.

BY 120 MM June 3, 1969 A. LORIA SILVER HALIDE EMULSION CONTAINING T DYE-FORMING COUPL Filed July 26, 1965 3,447,928 WO-EQUIVALENT YELLOW ER Sheet 2 of 2 m CURVE s 3 -fi 1 1 5 18 cunvs .1

v comma ICONTAINING z-squvwusnr a COUPLER I4 m Dl-g-BUTYLPHTHALATE 1- o E l '/z CURVE a COATING 2 SAME AS COATINGIBUI M) V h I CURVE s comma a coummms 4 -EQU|VALENT YELLOW-FORMING COUPLER m 1.2 Q Dl-g- BUTYLPHTHALATE Ma CURVE. 4 COATIN64SAMEASCOATIN63 BUT|=0 CURVE 4 7/ u .6 4 L 4 ,//I

EXPOSURE STEP Anflwnyloria INVENTOR BY MM ATTORNEJI AGENT United States Patent U.S. Cl. 96100 15 Claims ABSTRACT OF THE DISCLOSURE Uncolored open-chain reactive methylene two-equivalent yellow dye-forming couplers having one of the hydrogens of the active methylene group replaced with an acyloxy substituent have good coupling reactivity with oxidized primary aromatic amine color developing agents to form good yellow dye images and are advantageously incorporated in light-sensitive photographic silver halide emulsion layers to form yellow dye images.

This is a continuation-in-part of Loria U.S. Ser. No. 246,931, filed Dec. 26, 1962, now abandoned.

This invention relates to photography and particularly to compounds which form dyes upon coupling with oxidized color developing agent and to photographic elements containing these compounds.

The formation of colored photographic images by the coupling of oxidized aromatic primary amino developing agents with color forming or coupling compounds is well known. In these processes the subtractive process of color formation is ordinarily used and the image dyes are intended to be cyan, magenta, and yellow, the colors that are complementary to the primary colors. Usually phenol or naphthol couplers are used to form the cyan dye image, pyrazolone couplers are used to form the magenta dye image and couplers containing a methylene group having one or two carbonyl groups attached to it are used to form the yellow dye image.

In these color developing processes the color forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer so that during development it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development. DiflFusible type couplers are used in color developer solutions. Fischer type couplers and nonditfusing couplers are incorporated in photographic emulsion layers. When the dye image formed is to be used in situ, couplers are selected which form nondiifusing dyes. The dye image used for image transfer processes should be diffusible but capable of being mordanted or fixed in the receiving sheet. For this purpose a coupler is selected which will produce this type of dye.

Conventional color-forming couplers are four-equivalent, that is, they require the development of four rnols of exposed silver halide in order to supply one mol of oxidized color developing agent that is free to couple and form one mol of dye. Two-equivalent couplers require the development of only two mols of exposed silver halide to bring about the formation of one mol of dye. Twoequivalent couplers are very desirable for color photography, since only one-half the usual amount of silver halide is needed and the light-sensitive coatings can thus be made thinner. Certain of the available two-equivalent couplers tend to produce more stain than is desired, and

others have not had the desired coupling reactivity. New classes of two-equivalent couplers are needed.

It is, therefore, an object of my invention to provide a new class of colorless two-equivalent dye-forming couplers which have a high degree of reactivity.

Another object is to provide a new class of dye-forming twoequivalent couplers which not only have a high coupling reactivity but which do not produce stains caused by nonirnage forming coupling that is a problem with some of the prior art two-equivalent couplers.

Another object of my invention is to provide valuable acyloxy substituted two-equivalent couplers for forming dye images that have good spectral absorption characteristics, and good stability to prolonged exposure to light, heat, and high humidity.

Another object is to provide acyloxy substituted twoequivalent couplers which have good coupling reactivity and which include the diffusible type coupler, the Fischer type and the nondiffusing type couplers which are readily incorporated in light-sensitive hydrophilic colloid-silver halide emulsion layers in a wide range of coupler to solvent ratios.

Still another object is to provide photographic hydrophilic colloid-silver halide emulsion layers containing my acyloxy substituted twoequivalent couplers.

These and other objects will appear from the following specification and claims.

These and other objects are accomplished by the synthesis and use of my novel couplers. The couplers of my invention are open-chain reactive methylene two-equivalent couplers wherein one of the hydrogens of the active methylene group is replaced with an acyloxy substituent. The acyloxy group includes, for example, unsubstituted and substituted alkylacyloxy, arylacyloxy, and heterocyclicacyloxy. These groups may be either monoor divalent, i.e., they can contain either one or two coupler moieties. The efiectiveness of my couplers as two-equivalent couplers is not dependent on the specific composition of the coupler moiety, and it will be understood that this moiety may be varied widely to meet such requirements as spectral absorptivity, reactivity, solubility, and ditfusibility, as may be imposed by the photographic system in which the couplers are to be used. Typical examples of different classes of couplers which are included in my invention are alpha-acylacetamides, 2-(alpha-cyanoacetyl)coumarones, and alpha-acylacetonitriles, etc. My two-equivalent couplers are derived to advantage from any of the known four-equivalent open chain reactive methylene couplers.

Accordingly, the couplers of my invention may be further represented by the following general formula:

RC O in wherein n represents an integer of from 1 to 2; R represents an alkyl radical (either a straight or branched chain alkyl radical of from 1 to 30 carbon atoms, a monoor bicyclic alkyl radical such as cyclohexyl, terpenyl, such as, a norbornyl radical, etc., said alkyl radicals being unsubstituted or substituted alkyl radicals, containing substituent groups such as halogen, nitro, 'hydroxyl, carboxyl, amino, substituted amino, aryl, carboxyl esters (e.g., carboethoxy, carbophenoxy, etc.), amido (e.g., acetamido, butyramido, ethylsulfonarnido, N-propylbenzamido, etc.), carbamyl (e.g., N-methylcarbamyl, N-octadecylcarbamyl, N-methyl-N-phenylcarbamyl, etc.), sulfarnyl (e.g., N- propylsulfamyl, N-tolylsulfamyl, etc.), alkoxy (e.g., ethoxy, octadecoxy, etc.), aryloxy (e.g., phenoxy, tolyloxy, etc.), sulfo, sulfoesters (e.g., methylsulfonyl octadecylsulfonyl, ethoxysulfonyl, dodecoxysulfonyl, phenylsulfonyl, tolylsulfonyl, phenoxysulfonyl, etc.), an aryl radical such as phenyl or naphthyl, said aryl radicals being unsubstituted or substituted with groups such as defined above for the substituted alkyl groups, and a heterocyclic radical containing a heterocyclic ring with to 6 atoms in the ring, typical radicals including furanyl, ben- Zofuranyl, benzothiazolyl, naphthothiazolyl, thiazolyl, benzoxazolyl, oxazolyl, imidazolyl, quinolyl, pyridyl, etc., said heterocyclic groups being unsubstituted or substituted with groups as defined for the substituted alkyl groups above; R represents the cyano group, a carbamyl group (e.g., an unsubstituted carbamyl), an alkyl carbamyl group in which the alkyl group is either straight or branched chain having from 1 to 30 carbon atoms, a monoor bicyclic group such as cyclohexyl, terpenyl (e.g., a norbornyl group, etc.), a dialkylcarbamyl group in which a combination of any two of the above-mentioned alkyl groups are substituted on the nitrogen atom of the carbamyl group, an aryl-carbamyl group in which the aryl group is a group such as phenyl, naphthyl, etc., an aralkylcarbarnyl group in which a combination of any two of the above alkyl and aryl groups are substituted on the nitrogen atom of the carbamyl group (e.g., an N-methyl-N-phenylcarbamyl group, an N-butyl-N-tolylcarbamyl group, etc.), a heterocyclic carbamyl group in which the heterocyclic group is a group having a heterocyclic ring with 5 to 6 atoms in the ring, typical radicals including a thiazolyl group, a benzothiazolyl group, a naphthothiazolyl group, an oxazolyl group, a pyridyl group, a quinolyl group, etc., an alkyl heterocyclic carbamyl group in which a combination of any two of the above alkyl groups and heterocyclic groups, respectively, are substituted on the nitrogen atom of the carbamyl group (e.g., an N-(Z-benzothiazolyl)-N-methylcarbamyl group, etc.), an aryl heterocyclic carbamyl group in which a combination of any two of the above aryl groups and heterocyclic groups, respectively, are substituted on the nitrogen atom of the carbamyl group (e.g., an N- phenyl-N-(2-thiazolyl)carbamyl group, etc.), in which the alkyl, aryl, and heterocyclic groups on the carbonyl are unsubstituted or substituted with groups such as defined for substituted alkyl in R above; R when n is the integer 1, represents an alkyl, aryl, or heterocyclic group as defined in R above, and, when n is the integer 2, R represents alkylene (e.g., ethylene, hexylene, etc.), arylene (e.g., 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthy1ene, ethylenebis 1,4-phenylene), sulfonylbis(1,4-phenylene), etc.), a divalent heterocyclic radical o t-csnngocno ONH derived from any of the heterocyclic groups defined above for R (e.g., a 3,5-pyridylene, a 4,8-quinolylene, a 4,5- thiazolylene, a 5,6-benzothiazolylene, a 6,7-naphthothia- 4 zolylene, a 4,5-oxazolylene, a 4,5-in1idazolylene, etc.), the said alkyl, aryl and heterocyclic groups being unsubstituted or substituted with any of the groups such as defined for substituted alkyl in R above.

My two-equivalent couplers are characterized by having an acyloxy group on the coupling position of the coupler which gives them good coupling activity and other valuable properties. Nonimage-forming but stainproducing reactions characteristic of certain prior art twoequivalent couplers are not exhibited by my couplers. Some of my nonditfusible couplers have good coupling reactivity when incorporated in emulsion layers with no high-boiling coupler solvents, while the others are dispersed to advantage in high-boiling solvent solutions in a wide range of coupler to solvent ratios.

The acyloxy group provides a means of attaching other substituents to my couplers such as, for example, preformed dyes useful in color correction, dye transfer processes, and the like. Additional ballasting groups can also be conveniently introduced via the acyloxy group. Such groups, i.e., preformed dyes, ballasting groups, etc., are then eliminated during the coupling reaction of my couplers with oxidized color developer which forms the image dyes.

The following typical couplers will serve to illustrate but not limit my invention.

( 1 u-Acetoxy-a-benzoylacetanilide (3511 0 0 CH0 ONHC5H5 C O C H:

COOH

(7) a-(fl-Carboxypropionyloxy) -a-{3- u- (2,4-di-tertamylphenoxy) butyramido] benzoyl}-2-methoxyacetanilide COOH CHa?

(8) :x-Acetoxy-a-(Z-methoxybenzoyl)-4-[2-(2,4-di-tertamylphenoxy-S- 3-sulfobenzamido benzabido] acetanilide sodium salt I S O N8- O C 0 CH3 l a a-t aromatic amino color-forming silver halide developing agents such as the phenylenediamines, e.g.,

the p-aminophenols and their substitution products where the amino group is unsubstituted may be used in the alkaline developer solution with my couplers. Various other materials may be included in the'developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulfite, bromide, iodide, etc., and the thickening agents used in viscous developer compositions such as carboxymethyl cellulose, carboxyethyl cellulose, etc. The following is a typical developer solution given to illustrate but not limit the invention.

2-amino-S-diethylaminotoluene HCl g.. 2.0 Sodium sulfite (anhydrous) g 2.0 Sodium carbonate (anhydrous) g 20.0 Potassium bromide g 1.0 Coupler g 2.0 Water, to ml 1000.0

The other coupler examples used to illustrate my invention are nondifiusing and are used to advantage in photographic emulsion layers. Couplers such as 7 and 8 illustrate those that are incorporated as Fischer type couplers. The other nondiffusing couplers are incorporated in emulsion layers by methods such as are described by Mannes et a1. U.S. Patent 2,304,939, issued Dec. 15, 1942, Jelley et a1. U.S. Patent 2,322,027, issued June 15, 1943, etc., in which high-boiling organic solvents are used to dissolve the coupler, and by methods described in Vittum et a1. U.S. Patent 2,801,170, and Fierke et al. U.S. Patent 2,801,171, both issued July 30, 1957, and Julian U.S. Patent 2,949,360, issued Aug. 16, 1960 in which low-boiling or water-soluble organic solvents are used with or in place of the highboiling solvent. Not only can emulsion layers containing my couplers be made thinner because they require only one-half the silver halide required by conventional couplers (i.e., four-equivalent couplers) but some of my couplers are sufficiently reactive that they do not require any highboiling coupler solvent that is usually required by couplers. Thin image-forming layers are very desirable because they cause less light scattering and produce sharper images.

My nondifiusing couplers and 6 form diffusible dye images upon color development and are used to advantage either in image transfer elements or in emulsion layers that contain my coupler as a nonimage-forming competing coupler along with an image-forming coupler. Couplers and 16 have a sulfamyl group (on a noncoupling position) which ionizes and forms a diffusible dye upon color development at a pH above 11.

The other nondifiusing couplers used to illustrate my invention form nondifiusing dyes and are used to advan tage in any photographic element where incorporated image-forming couplers are desired. Couplers No. 15 and 16 when developed with a color developer with a pH lower than 11 will produce nondiffusing dye images.

Couplers 30, 31 and 32 form magenta image dyes on coupling with oxidized color developer.

My couplers are used in the color development of photographic hydrophilic colloid-silver halide emulsion layers of the developing-out type either in the color developer solution or in the emulsion layer. The emulsions may contain silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromo iodide, etc., as the light-sensitive material.

Hydrophilic colloids used to advantage include gelatin,

H colloidal albumin, a cellulosederivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in U .S. Patent 2,286,215, of Lowe; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of .19 26% as described in US. Patent 2,327,808 of Lowe and'Clark,

a water-soluble ethanolamine cellulose acetate as described in U.S. Patent 2,322,085 of Yutzy; a polyacrylamide having a combined acrylamide content of 3060% anda specific viscosity of 025-15 on an imidized polya'crylamide of like acrylamide content and viscosityas described in U.S. Patent 2,541,474 of Lowe, Minsk and Kenyon; zein as described in U.S. Patent 2,563,791 of Lowe; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in U.S. Patent 2,768,154 of Unruh and Smith, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyano-acetate copolyrner as described in U.S. Patent 2,808,331 of Unruh, Smith" and Priest; or a polymeric material which results from polymerizing a protein or a saturated acrylated protein with a monomer having a vinyl group as described in U .8. Patent 2,852,382 of Illingsworth, Dann and Gates. I

The emulsions used in the photographic element of my invention can be chemically sensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be, added, such as those described in Sheppard U.S. Patent 1,574,944; Sheppard and Punnett U.S. Patent 1,623,499; and Sheppard and Brigham U.S. Patent 2,410,689. a

The emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060 and as anti'foggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245 and 2,566,263.

The emulsions can also be chemically sensitized with gold salts as described in Waller, Collins and Dodd U.S. Patent 2,399,083 or stabilized with gold salts as described in Damschroder U.S. Patent 2,597,856 and Yutzy and 'Leermakers U.S. Patent 2,597,915. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride andv 2-aurosulfobenzothiazole methochloride.

The emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U.S. Patent 2,487,850), polyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925), or bis(fl-aminoethyl)sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926).

The emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, 1,846,302 and 1,942,854; ,White U.S. Patent 1,990,507; Brooker and White U.S. Patents 2,112,140, 2,165,338, 2,493,747 and 2,739,964; Brooker and Keyes US. Patent 2,493,748; Sprague U.S. Patents 2,503,776 and 2,419,001; Heseltine and Brooker U.S. Patent 2,666,761; Heseltine U.S. Patent 2,734,900, Van Lare U.S. Patent 2,739,149; and Kodak Limited British 450,958.

The emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623; Carroll and Allen U.S. Patent 2,288,226; and Carroll and Spence U.S. Patent 2,334,864; and the polyethylene glycol type-of Carroll and Beach U.S. Patent 2,708,162.

The above-described emulsions can be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film, and related films of resinous materials, as Well :as paper, glass and others.

The couplers of my inventionmay also be used to advantage in image-forming layers, either alone or with image-forming compounds other than silver halide such as ZnO, ZnS, CdS, CdSe, NiS, etc., either with or without binders such as gelatin, polyvinyl alcohol, etc.

Usually my emulsions are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support. Usually the support is coated in succession with a redsensitive layer, a green sensitive layer and a blue-sensitive layer either with or without a Carey Lea filter layer between the blue-sensitive and green-sensitive layers. The three differently color sensitized layers may be arranged in any other order over one another that is' desirable;

10 ml. of a gelatino-silver halide emulsion with stirring at 40 C. The resultant emulsion was coated at 0.009 inch wet thickness.

An image exposed strip of this coating was processed by contacting it for 7 minutes at 80 F. with a mordant containing receiving sheet which had been presoa-ked in the following developer solution:

Developer formula Sodium carbonate monohydrate g 22.000 Ascorbic acid g 0.385 Potassium bromide g 0.825 Sodium sulfite g 2.000 4 [N Ethyl N (Beta hydroxyethyl)- amino] g-.. 11.000 Water, to pH 11.0 m1 1100.000

- The following photographic data were obtained from the processed strips, i.e., from the mordant receiving sheets containing the transferred dye images.

Light Fade to Heat Fade:

Xenon Arc 140F., 70% RH.

Specular Mordant in Receiving Sheet 7 D m Am hrs. 70 hrs. 1 wk. 2 wks. Dens ty Dimethyl-fi-hyiiroxyethyl-airfitaideeylami 0 r0 ammonium 0 en phospli tePX Z. 437 .15 .38 .13 .30 .86 Octadecyltributylammonium thiogyanateiz-l jtdihexgdtelpyl-L tdiazio;

ieye o octane i iocyana e 2,4-ditert-amylpl1enol .80 434 .11 .32 0 0 .81

EXAMPLE 2 however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer. Preferably, these light-sensitive layers are arranged on the same side of the support.

Elements made for image transfer processing may use a separate reception sheet which is contacted with the light-sensitive layer during its development or the reception layer may be an integral part of the light-sensitive element. Any of the support materials mentioned previously may be used for a separate reception sheet. The reception layer comprises a hydrophilic colloid layer containing a cationic mordant, e.g., the polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk US. Patent 2,882,156, granted Apr. 14, 1959. Other mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al. US. Patent 2,484,430, granted Oct. 11, 1949, and cetyl trimethyl ammonium bromide, etc. Particularly effective mordanting compositions are described in copending applications of Kneckel et al. US. Ser. No. 211,095, filed July 19, 1962, now US. Patent 3,271,148 and Bush US. Ser. No. 211,094, filed July 19, 1962. now US. Patent 3,271,147. Additional variations of the image transfer elements and processes in which couplers of my invention (such as 5, 6, 15, 16 and 37) can'be used to advantage, are described in copending application of Whitmore and Mader U.S. Ser. No. 222,105, filed Sept. 7, 1962, now US. Patent My invention is still further illustrated by the following typical examples.

EXAMPLE 1 To a solution of 0.32 g. of Coupler No. 6 in 10 ml. of water, 6 drops of 10% sodium hydroxide, 13 ml. of 10% bone gelatin and 1 g. of 5% formalin was added posures on a 1B intensity scale sensitometer and processed:

through the following process.

Process steps Time:

30" Water dip. 10' Development. 5 Stop bath. 5' Ferricyanide bleach.- 5' Wash. 5' Fixing bath. l0 Wash.v

30 Photo 'Flo (wetting agent 7 solution) dry.

The following developer solutions were used 'in this processr p r Developer 1 Sodium sulfite 2 g 2. Z-amino-5-diethylaminotoluene HCl g 2 Sodium carbonate "g" 20 Potassium bromide g -2 Water, to pH 1.0.86

' 4-amino-N-ethyl-3-methyl-N-(fi-meth- Developer 2 ylsulfonamidoethyDaniline g 50.00 Benzyl alcohol mL- Water, to make ml 1000.00 Sodium sulfite g 2.00 N ethyl N (beta methanesulfonamidoethyl) Acid stop bath 4-aminoaniline sulfate 5.00 5 m1 8 6 Sodium carbonate g 50.00 Acetlc acld (glaclal) Sodium bromide 86 W r, to k ml 100% Sodium hydroxide (20% solution) ml 4.00 7 Sodium hexametaphosphate g 0.50 10 Formalm hardener Water PH 1075 L00 Formalin 37% by weight formaldehyde in The resulting yellow dye images were observed with a water) ml 20.00 spectrophotometer to determine the A values, and ex- Sodium bisulfite g 5.00 amined with a densitometer to obtain D values and Borax g 3.82 the density data needed to calculate the v and speed Sodium hydroxide g 4.50 values. These data are summarmized in Table I. Water, to make ml- 1000.00

TABLE I Coupler Developer Photographic Data Coating Gel, AgBr, Solvent, Formula Number mg./it. mg./ft. Coupler, mgJflifi mgJft. No. Am 1' Speed 386 145 90-001mm for 11- 45 1 453 2.08 2.37 ass 45 1 451 2.32 2.46 386 45 2 447 1.74 2.25 386 45 2 445 2.90 2.33 500 45 1 452 1 .ss 2 .33 500 45 1 453 3.06 2 .33 580 45 1 452 .59 580 45 1 442 1.08

The results obtained from coatings 1 through 6 show Ferricyanide bleach that in each instance the coating of my invention (i.e., 2, 4 and 6) with a two-equivalent coupler gave higher Pom-Slum ferilcyamde Sodium bromide 12.8 dye yields as evidenced by higher 7 and D values than Borax 7 3 were obtained with the corresponding control coatings B0 f ric acid g 15.0 No. 1, 3 and 5, respectively, with the corresponding four- Water to make m 1000 0 equivalent couplers even though the amount of silver halide used in these emulsion coatings was not limited. Hypo fix The results from coatings 7 and 8 further show the 500111111 sulfite g 5.90 advantage of coatings containing my two-equivalent cou- Sodium thiosulfate g 320.00 pler No. 10 compared to a four-equivalent coupler. S dium bisulfite 1.47 Water, to make m1 1000.00

EXAMPLE 3 Two multilayer coatings were prepared which were identical except that in the second one, i.e., coating No. 2, the silver halide level was reduced to one-half that contained in coating No. 1. These coatings each contained the four-equivalent coupler a-{3-[ot-(2,4-di-tert-amylphenoxy)butyramido]benzoyl} 2 methoxyacetanilide as a control coupler. A third coating, No. 3, was prepared which was identical to coating No. 2 excepting that an equimolar amount of coupler N0. 11 was used in place ofthe control coupler in the blue-sensitive layer. Each multilayer coating contained along with the yellow-forming layer, a light-sensitive layer with a magneta-forming coupler and one with a cyan-forming coupler.

Strips of these coatings were each given a blue light step tablet exposure in a sensitometer, and then processed as follows. Processing solution: Time in minutes Color developer 11.5

Acid stop bath 6.0 Formalin hardener 4.0 Water wash 4.0 Ferricyanide bleach 6.5 Water wash 4.0 Hypo fix 4.5 Water wash 8.0

The processing solutions had essentially the compositions set out below:

Color developer Benzyl alcohol ml 5.00 Sodium hexametaphosphate g 2.50 Sodium sulfite 1 g 2.50 Sodium bromide g 1.40 Potassium bromide mg 0.50 Sodium hydroxide g 13.10 Borax g 39.60

The yellow dye density to blue light in each step on the processed strips was measured with a densitometer and these density data were plotted against the step number of the step tablet. Consecutive steps represented 0.15 log exposure increments. A comparison of the yellow dye density curves 1 and 2 for the step tablet images obtained in coating No. 1 and No. 2, respectively, shows that the dye yield is proportional to the silver level in the coating. A comparison of the yellow dye density, curve 3, for the step tablet image obtained in coating No. 3 containing coupler No. 11 at the low silver level showed a high dye yield that was comparable to the yield obtained with coating No. 1 but with one-half the amount of silver that was used in coating No. 1.

The following example will illustrate the high reactivity of my couplers even in nonsolvent dispersions.

EXAMPLE 4 Two single layer coatings were made of a hydrophilic colloid-silver halide emulsion containing coupler 14. In coating No. 1 the coupler was dispersed as a solution in the high boiling coupler solvent, di-n-butylphthalate, at a coupler to solvent ratio of l: /2. In coating No. 2 this ratio was 1:0. These coatings contained 228 mg. of silver (as silver halide) and mg. of coupler per square foot. Similar coatings No. 3 and No. 4 were made containing equimolar amounts of the coupler a-pivalyl-Z-chloro-S- ['y- (2,4-di-tert-a-n1ylphenoxy)butyramido] acetanilide and silver at coupler to solvent ratios of l: /2 and 1:0, respectively.

Strips from each of these coatings were given identical exposures and processed as described in Example 3. The yellow dye density (to blue light) of each step on the processed strips was measured with a densitometor and plotted against the exposure step number.

The curves resulting from the plots of density vs. exposure showed that the strips containing coupler 14 gave 13 excellent dye image reproductions of the original step tablet image with very little diflFerence between the curves 1 and 2 for this coupler at coupler to solvent ratios of 1: /2 and 1:0, respectively. The curve 3 for the strip containing the dispersion of coupler a-pivalyl-2-chlor0-5-[v- EXAMPLE 6 Single layer coatings were made and coated to contain 400 mg. gelatin, 45 mg. of silver bromoiodide, 90 mg. of coupler, and either 45 mg. or mg. of di-n-butylphthalate (2,4-di-tert-amylphenoxy)butyramido]acetanilide in the P Square foot q These Weffi exposed and solvent at the ratio of 1: /2 had a substantially lower dye as dflscrlbed 111 f p 2 2; developer S0111 density at each step than the strip containing coupler No. t1011 The max vahle In and t max Value were 14. The curve 4 for the strip containing the nonsolvent measured and recorded 111 the followlng Table dispersion of the coupler used in coating No. 3 showed 10 TABLE 11 that there was very little dye produced and that no use- Dimbutyk ful image was produced of the original step tablet. Coating Coupler phthalate, x...

Similarly other couplers of my invention are used to Number u r rug/it. m Dm advantage .in hydrophilic colloid-silver halide. emulsions 1 17 45 449 2.68 when dispersed in coupler solvent solution or dispersed g g 2 12% 3-82 without coupler solvent and exhibit high reactivities. 4 1s 0 4 7 1:64

' 5 19 45 443 2. 39 EXAMPLE 5 9 a .2 as

Single layer coatings were made containing coupler No. g 32 222 f gg 16. Coating No. 1 contained 400 mg. of gelatin, 146 mg. 20 1g 21 0 447 4 silver bromoiodide, 63 mg. of coupler 16, and 31 mg. of 8 3 5%: di-n-butylphthalate per square foot of coating. Coating P 2 had same composltlon except.that 63 9 Similarly, the other couplers of my invention having dlethynauramlde per square foot of coatmg was used m Formula I are used to advantage in color photography as place of the d1-n-butylphthalate.

. 25 illustrated prev1ously with representative couplers.

35 smpsdof g were exgosed In eneral my couplers of Formula I are prepared processed to pro uce a non i usi e image ye as ea scribed in Example 2 using developer 1 for one strip and from the parent coupler havmg the formula developer'2 for another strip. Measurements made of (ID H A D the amount of light fade, that is, density H, loss i 33 p fi )ienon g wherein R and R are as described previously by first i fil 2 eat a at e enslty 31 3 replacing one of the hydrogen atoms on the active methyl- 8 fi stnp T g an ene group, with a halogen atom, (e.g., fluorine, bromine,

0 or one Wee are ta u a e as 0 chlorine, etc.) for example, by reacting the parent cou- 35 pler with a chlorinating agent, such as, thionyl chloride, Coating Developer Am: Llght Fade Heat Fade sulfuryl chloride, etc., as described by McCrossen, Vittum fig gg 8- 2? and Weissberger in US. Patent 2,728,658, issued Dec. 27, 1955, by reacting the sodium enolate of the parent 35 mm. strips of coating No. 2 were exposed and proc- 40 g i i wlthdperclilogyl g g i gi 2 essed. as described in Example 1 but using a mordanted mmen L ergefr receiving sheet presoaked in a developer solution having 19 y reactmg t e fif? brominatlng agent, such as, N-bromosuccmimide 1n acetlc the composition.

acid, etc., then by reacting the a-halo derivative of the Sodlufi} hyqroxlde coupler with the appropriate acylating agent, such as an ASCOTIPC 361d organic acid or alkhli metal salt of the organic acid g c f lgt having the formula:

0 mm su g 4-N-ethyl- N (fl-hydroxyethylamino)aniline g 2.0 (In) Water, to ml 1100. R2C

The dye transfer images formed in the mordanted re- OH ceiving sheets were measured for D A percent or I light fade after 30 and 100 hours exposure to a Xenon (IV) arc, and percent heat fade after 1 weekand after 2 weeks g storage in an oven at 140 F., 75% R.H. These values are summarized as follows:

D Perci ntii Light Peri en. Heat max Receiving Sheet Densili Mm e e Mordant and Support Units in m 30 hrs. 100 hrs. 1 wk. 2 wks.

N-cetyl-N-ethylmorpholinium ethosulfate methyltrilaurylammonium bromide eoacervate on a suitably subbed cellulose acetate sheet. 1. 47 436 6 19 18 33 Above mordant coacervate on white pigmented cellulose acetate support 2. 82 435 6 18 16 24 Poly(4-vinylpyn'dine) on White pigmented cellulose acetate support 1. 61 440 10 V 22 6 18 Couplers, such as No. 16 that have a sulfamyl group 65 wherein R is a defined previously and M represents an on a noncoupling position can be used to produce either a difiusible or a nondiifnsi-ble image dye. By using a high pH developer solution, this group ionizes (to the anion SO NH and this causes the dye to diffuse and tobe mordanted on a cationic type of mordant. If the pH of the. developer solution is kept low enough, e.g., below 11, the sulfamyl group does not ionize; consequently, the dye which is formed does not diffuse.

- The following example will illustrate the use of still "ther representative couplers of my invention.

alkali metal, such as, sodium, potassium, lithium, etc., in the presence of a suitable solvent, such as, acetic acid, glacial acetic acid, acetonit-rile, dioxane, tetrahydrofuran, diethylcellosolve, methylcellosolve, dimethylformamide, etc. It is preferable that the reactants be anhydrous. An amine, such as, triethylamine is used to advantage as a condensing agent in this reaction when the acylating agent is an organic acid. The reaction is usually conducted at an elevated temperature, e.g., the reflux temperature of the reaction mixture. The following preparation of cou- 15 16 pler 1 will illustrate the synthesis of my yellow-forming bring incipient crystallization. The solution was stirred couplers 1 and 41. while cooling to room temperature. The White crystal- Coupler 1 line product which formed was collected, washed on the funnel with cold water, and air dried. This solid was A mixture of 8 g. of u-benzoyl-a-chloroacetanilide recrystallized twice from absolute alcohol to yield a (prepared by the method given in McCrossen et a1. product which melted at 139139.5 C.

US, Patent 2,728,658, issued Dec. 27, 1955), 5 g. of Couplers 2 through 41 are prepared by similar reacanhydrous sodium acetate, and 150 ml. of acetic acid was tions using the coupler intermediate, acylating agent, refluxed for 18 hours. Sodium chloride began to separate condensing agent (where needed) and solvent reaction after about 3 hours of heating. Water was added to the medium listed in Table III. The melting points found hot solution to just dissolve the sodium chloride and for my couplers are given in Table III.

TABLE 111 Solvent M.P. of Compound Condensing (Reaction Product No. Coupler Intermediate Acylating Agent Agent Medium) C.) 1 az-B enzoyl-a-chloroacetanilide Sodium acetate Acetic acid 139-139. 5 2 a-Benzoyl-a-fluoro-o-methoxy aeedo 128-129 tanilide (Loria et al., U.S. Serial No. 51,549, filed August 24, 1960). 3 a-B euzoyl-a-bromo-3,5-dicarbo- -do -do..... 169-171 methoxyacetanilide. 4 a-B enzoyl-a-bromo-3,o-dicarboxy- 108-110 acetam'lide. 5 do Sodium stearate Dimethylformamide..- 200 6 a-Bromo-a-plva1yl-3,5-dicarboxym-Pentadecylphenoxy acetic acid so- Ethyl alcohol 90 acetauilide. dium salt (Bush at al., U.S. 2,908,-

573, issued October 13, 1959). 7 a-Chloro-at-l3-[z-(2,4-di-tert-amyl- Succinic acid monosodium salt Dioxane 180 phenoxy)butyramido]benzoyl}-2- methoxyacetanilide (McCrossen et al., U.S. Patent 2,875,057, issued February 24, 1959). 8 a-Chloro-a-(o-methoxybenzoyl)-4[2- Sodium acetate Acetic acid 170 (2,4-di-tert-amylphenoxy)-5-(3- suliobenzamido)benzamidolacetanilide sodium salt. 9 a-Chloroa-(2-methoxybenzoyD-4-[ado ..do 91-92 (2,4-di-tert-amylpheuoxy)butyramido]acetanilide (Yule U.S. 2,407,- 211, issued Sept. 3, 1946 and Lorie et al., U.S. 2,728,659, issued Dec. 27,

1955). 10 a-Benzoyl-a-chloro-2-methoxyacetan- Stcaric acid Triethylamine Acetonitrile 66-68 ilide. 11 As in Compound 7 above Acetic acid do do 200 12.. a-Chloro-a-{3-[ -(2,4-di-tert-amyl- .....do do do 98-99 phenoxy)butyramido]benzoyl]-2- methoxyacetanilide. As in Compound 12 above Pivalic acid do do 107-108 As in Compound 2 above a-(2di-n-amfgphenoxy)acetic acid Dimethylformamide..-- 89-91 so mm sa 15 a-gelnzoyl-a-chloro-4sulfamylacetan- Stearic acid Triethylamine ..do 116-118 1 e. 16 a-ghdloro-a-pivalyl-4-sulfamylacetaudo do ..do-.. 108-110 1 e. 17 a-Benzoyl-a-fluoro-2-chloroacetanilide Sodium stear do 62-63 (Loria U.S. Serial No. 51,549). 4 18 As in Compound 2 above a-(2,4-di-tert-amylphenoxy)acetic Acetonitrlle 106-108 acid (McCrossen et al., U.S. 2,875,- 057, issued Feb. 24, 1959 and Mc- Crossen et al., U.S. 2,728,658, issued Dec. 27, 1955). 19 As in Compound 2 above. As in Compound 6 above Ethyl alc0l1ol 82-87 20 cz-B enzoyl-wfiuoro3-chlor Sodium stearate Dimethyliormamlde 75-77 21 As in Compound 2 above... a-(2,4-di-tert-amylphenoxy) butyrlc .do 123-125 acid sodium salt. 22 As in Compound 2 above 4-[a-(2,4-di-tert-amylphenoxy)aceta- Triethylamine Acetom'tnle 161-162 mido] benzoic acid. 23 a-IQflOIO-a-PW3.131-2-0111010 acetania-(2,4-di-n-amylphenoxy) acetic acid ..do Dimethylformamlde.-.. 52-54 1 e. 24 As in Compound 2 above Z-furoic acid o ..do 25.. As in Compound 7 above --do ..do Acetonitrile 26 a-Benzoyl-a-chloro-N-(4,5-dicar- Sodium st Dimethylformamlde bethoxy-2-thiazolyl) acetamide. 27 a-Chloro-a-pivalyl-N-(5carbethoxy -do do 2-thiazolyl)acetamide. 28 a-Brotmo fi-pivalyl-N-(2-pyridinyl)- As in Compound 6 above.- Ethyl alcohol 2.06 211111 9. 29 a-Bromo-a-pivalyl-N,N-bis(car- Sodium stear te Dimethyliormamide.-.. bethoxymethyDacetamide. j 30 a-Chloro-a-(B-naphthoyl)acetonitrile ..do DioYaoo 31-. As in Compound 30 above.. Sodium acetate.-- Acetic acid 32.- a-Chloro-a-cyanoacetylcoumarone..- Sodium stearate Dimethy lformamidm- 33 As in Compound 2 above 5-(3-ch1orosulfony1benzamido) Ethyl alcohol 180 di-tertamylphenoxy)benzoic acid (with subsequent acid hydrolysis o1 chlggosulfonyl group to sulfonic aci 34 a-Chl oi t yz pivalyl-ti,s-dicarboximido- Stearic acid Triethylamine Dimethylformamide.--- 118-120 8136 a 8. 35 a-Chloro-a-pivalyl-3-chloroacetanilide ..do .do do 36 a-Chloro-a-pivalyl4(N,N-dimethyl- ..-..do-- do 100-101 suliamyl) acetanilide. 37 a-Chloro-a-pivalyl-4-(methylsulfondo do 74-76 amido)acetanilide. 38 a-BeIlZOYl-a-Ch101'0-3-ch1010-2- ..-.do do ..do 72-74 methoxyacetanilide. 39 a-Benzoyl-a-chloroaceto-o-toluidide do do do 81-82 40 a-Chloro-a-pivalyl-2-chloro-5-[6-(2,4- Benzoic acid do 140-142 di-tert-amylphenoxy)butyramido1- acetanilide. 41 As in Compound 40 above Sodium acetate Acetic acid 77-79 42 a-Chloro-a-(3-dodecanamidobenzoyl)- Octanoic acid. Triethylamiue Acetonitrile. 67-69 Z-methoxyacetanilide. 43 As in Compound 10 above 'letradccauedioic acid ..do ..do

Decomposition.

My invention is still further illustrated by the accompanying drawings FIG. 1 and FIG. 2.

FIG. 1 shows the curves 1, 2 and 3 representing yellow dye image density to blue light vs. exposure obtained for coatings l, 2, and 3, respectively, described in Example 3.

FIG. 2 shows the curves 1, 2, 3 and 4 representing the yellow dye image density to blue light vs. exposure ob tained for coatings 1, 2, 3 and 4, respectively, as described in Example 4.

The two-equivalent image-forming couplers of my invention are distinguished from other two-equivalent couplers by having an acyloxy group substituted on the coupling position of the coupler molecule. My couplers are characterized by not producing stain, a problem with certain prior art two-equivalent couplers, and by having very good coupling reactivity. My nondiffusing couplers are dispersed readily in emulsion layers as a coupler solvent solution having .a wide range of coupler to solvent ratios.

My couplers are not only valuable for the reasons cited but because photographic emulsion layers color developed with them require only /2 the amount of silver halide required by four-equivalent couplers. Of particular value are certain of my nondiffusing couplers which have high coupling reactivity when dispersed in photographic emulsion layers without any high boiling solvent. These couplers are coated to advantage in particularly thin layers that produce good sharp images.

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim:

1. A yellow dye image-forming layer containing lightsensitive silver halide emulsion and an uncolored twoequivalent coupler which is capable of forming a yellow dye on coupling with the oxidation product of a primary aromatic amino color developing agent, said coupler containing at least one open-chain reactive methine group joined directly to two activating groups, at least one of said activating groups being a carbonyl group, said active methine group also joined directly to an acyloxy group, which acyloxy group is eliminated on the coupling of said coupler with said oxidation product.

2. A yellow dye image-forming layer containing lightsensitive silver halide emulsion and an uncolored two equivalent yellow dye-forming coupler of the formula:

wherein n represents an integer of from 1 to 2; R represents a group selected from the class consisting of an alkyl radical, an aryl radical, and a heterocyclic radical containing a 5 to 6 membered heterocyclic ring; R represents a group selected from the class consisting of a carbamyl radical and the cyano radical; R represents, when n is the integer 1, a group selected from the class consisting of an alkyl radical, an aryl radical, and a heterocyclic radical containing a 5 to 6 membered heterocyclic ring, and, when n is 2, a group selected from the class consisting of an alkylene radical, an arylene radical, and a divalent heterocyclic radical.

3. A yellow dye image-forming layer of claim 2 in which the silver halide is in a gelatin silver halide emulsion.

4. A multilayer, multicolor photographic element containing silver halide and incorporated image dye-forming couplers which are capable of forming dyes on coupling with the oxidation product of a primary aromatic amino color developing agent, said element containing for the formation of yellow image dye a coupler containing at least one open-chain reactive methine group joined directly to two activating groups, at least one of said activating groups being a carbonyl group, said active methine group also joined directly to an acyloxy group, which acyloxy group is eliminated on the coupling of said coupler with said oxidation product.

5. A multilayer, multicolor photographic element containing silver halide and incorporated image-dye-forming couplers which are capable of forming dyes on coupling with the oxidation product of a primary aromatic amino color developing agent, said element containing for the formation of yellow image dye a coupler of the formula:

wherein n represents an integer of from 1 to 2; R represents a group selected from the class consisting of an alkyl radical, an aryl radical, and a heterocyclic radical containing a 5 to 6 membered heterocyclic ring; R represents a group selected [from the class consisting of a carbamyl radical and a cyano radical; R represents, when n is 1, a group selected from the class consisting of an alkyl radical, an aryl radical, and a heterocyclic radical containing a 5 to 6 membered heterocyclic ring, and when n is 2, a group selected from the class consisting of an alkylene radical, an arylene radical, and a divalent heterocyclic radical.

6. An image-forming layer of claim 2 in which the R group of the uncolored two-equivalent coupler formula is an alkyl radical, said layer containing a light-sensitive hydrophilic colloid-silver halide emulsion.

7. An image-forming layer of claim 2 in which the R group of the uncolored two-equivalent coupler formula is a pivalyl radical, said layer containing a light-sensitive hydrophilic colloid-silver halide emulsion.

8. An image-forming layer of claim 2 in which the R group of the uncolored two-equivalent coupler formula is an aryl radical, said layer containing :a light-sensitive hydrophilic colloid-silver halide emulsion.

9. An image-forming layer of claim 2 in which the R group of the uncolored two-equivalent coupler formula is a heterocyclic radical, said layer containing a lightsensitive hydrophilic colloid-silver halide emulsion.

10. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing as the sole dye image-former the two-equivalent coupler alpha-acetoxy-alpha-{3-['y- (2,44ii-t-amylphenoxy)butyramido] benzoyl}-2 methoxyacetanilide.

11. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing as the sole dye image-former the two-equivalent coupler alpha-benzoyl-alpha-[alpha- (2,4-di-n-amylphenoxy)acetoxy]-2-methoxyacetanilide.

12. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing as the sole dye image-former the two-equivalent coupler alpha-pivalyl-alpha-stearoyl- 0xy-4-sulfamylacetanilide.

13. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing as the sole dye image-former the two-equivalent coupler alpha-pivalyl-alpha-[alpha-(3- pent adecylphenoxy) acetoxy] -3 ,S-dicarb oxyacetanilide.

14,. A light-sensitive hydrophilic cololid-silver halide emulsion layer containing as the sole dye image former the two-equivalent coupler alpha-acetoXy-alpha-{3-[alpha- (2,4-di-t-amplphenoxy)butyramido1benzoyl} 2-methoxyacetanilide.

(15. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing as the sole dye image-former r 19 20 the; two-equivalent 1 coupler alpha-(3-dqqecanamidoben- FOREIGN PATENTS zoyl)alpha-octanoyloxy-Z-methoxyacetamhde. 648,907 1/1951 Great B a n- References Cited UNITED STATES PATENTS I. TRAVIS BROWN, Primary Examiner. I r

3,180,734 4/1965 Willems et a1 96-100 CL 3,271,152 9/1966 Hanson 96100 3,311,476 3/1967 Loria 96-55 9655, 56.3, 56.4, 74 

